Treatment of wool-containing textile materials and products thereof



United States Patent *Ofiice 2,723,924 Patented Nov. 15, 1955 TREATMENTOF WOOL-CONTAINING TEXTILE MATERIALS AND PRODUCTS THEREOF Herbert W.Mackinney, Pines Lake, N. 1., assignor to Union Carbide and CarbonCorporation, a corporation of New York No Drawing. Application February3, 1953, Serial No. 334381 6 Claims. (11. 117-141 This invention relatesto the treatment of wool and wool-containing textile materials forshrink-proofing the wool and for rendering the same resistant tofelting; and more especially it concerns a novel process whereby wool orwool-containing textile articles are stabilized against undue shrinkageand felting during the service life of textiles made therefrom. Theinvention includes the wool-containing textile article thus stabilized.

The strong tendency of wool and wool-containing textile articles toshrink and to felt upon washing thereof during their service life haslong beenknown. Numerous attempts have been made to overcome in somedegree these objectionable characteristics of wool and wool-containingtextiles. While some treatments of wool have provided some improvementin such-properties of the wool none have been entirely satisfactory,often because of the sacrifice of some other desired property of thetextile, or due to lack of permanence of, the shrinkproofing.

The invention isbased in important part upon the discovery that whenwool or a, wool-containing textile is treated with a mildly acidicsolution of certain hereindescribed novel resins, the resin is adsorbedon the sur faces of the wool, and upon being converted thereon to theinfusible insoluble form, adheres tenaciously to the wool and confersthereon the property of resisting felting and shrinking duringlaundering. The invention has the further advantages that .it isapplicable to wool in any form, such as fibers, yarns, or woven orknitted textiles, as well as to mixtures of wool with other textilematerials such as cotton, nylonQdynel, fOrlon, etc. No squeeze rolltreatment or the equivalent is necessary to remove excess of the resincomposition and hence the hand of the wool is not deleteriously affectedand interfiber bonding does not occur. The complete treatment isconducted at moderate temperatures in very dilute aqueous solutions,hence the wool is not exposed to high temperatures. during thisanti-felting treatment. The process readily can be conducted in simpleapparatus such as that used for dyeing. The resin treatment preferablyis applied to the wool or wool-containing textile after dyeing andfulling.

In the practice of the invention the wool or woolcontaining textilearticle is wetted with water containing suflicient of a hydrogen halideor a lower fatty acid having one to five carbon atoms to adjust the bathto a pH within the range from 3 to 6. The wetted wool is then heatedwithin therange C. to 100 C. and preferably around 50 C. to 70 C. in amildly acidic aqueous solution containing a salt of a novel polyaminopolyhydroxy resin until the adsorption of the resin is complete. Thissolution essentially comprises enough water acidified with a hydrogenhalide or a lower fatty acid ofone to five carbon atoms to provide a pHbetween 3 and 6 to cover the article being treated, together with asuitable quantity of an acid soluble resin of the type hereinafterdescribed. Preferably the solution also contains suflicient of an in-Relaxation shrinkage can be eliminated solubilizing agent such asformaldehyde, glyoxal or a water soluble aliphatic diepoxy compound suchas diglycidyl ether and ethylene glycol diglycidyl ether to promoteadherence of the resin upon the article. A small amount of non-ionicwetting agent preferably also is present. The quantity of resin usedincreases with the fineness of the wool fibers being treated, and withthe extent of surface damage in the case of reprocessed wool. An amountof resin between 3% and 12% of the dry Weight of the wool orwool-containing article generally is sufiicient. When used, the amountof insolubilizing agent can vary considerably. Excellent results aresecured when it is about one-third of the weight of the resin used.After the resin solution has been suitably adsorbed by the fibers, whichcommonly is effected in one to two hours, the treated article is removedfrom the solution and excess treating liquid is drained off. When anexcess of the resin over that adsorbed by the fibers is present, theheated article is then thoroughly rinsed with water to remove excesstreating agent.

The final conversion of the resin to the insoluble, infusible form afterits adsorption by the wool fiber preferably is effected at ambienttemperatures, using a cold dilute alkaline aqueous solution containingsulficient of an alkaline compound, such as an hydroxide, carbonate orbicarbonate of an alkali metal, a tertiary amine and the like, to adjustthe pH of the solution to at least 8.

The solution also contains an insolubilizing agent of the classconsisting of formaldehyde, glyoxal and the water soluble diglycidylcompounds recited hereinbefore. This conversion solution contains fromabout 1% to' about 5% of each of the said alkaline compound and theinsolubilizheating the resin-treated article to temperatures of 200 F.to 300 F. or somewhat higher in the presence of a' small amount; e. g.1%, of one of the. insolubilizing agents. I

The treated article then is rinsed with'water and dried, preferablyuntensioned. i

If desired, the solution of resin and insolubilizing agent can beapplied to the wool containing article by the well known paddingtechnique, in which case the padding is done at or about roomtemperature, and the padding solution preferably contains a non-ionicwetting agent. The paddedarticle is dried at temperatures commonlyaround 220 F. to 3-00 F. to convert the resin to the insoluble form,after which the article is scoured with. a detergent and dried in theuntensioued state. In this procedure the solution remaining in the clothdeposits some resin on the fiber in massive form which then bonds onefiber to another and causes stiffening. This padding method is thereforeused only when such stiffening is desirable. 1

The novel resinsemployed in this invention are the chemically reactiveresinous products soluble in acidic aqueous solution which are preparedby reacting aryl polyepoxides at elevated temperatures with the saltsresulting from the neutralization of aliphatic polyamines with fattyacids having from 2 to 5 carbon atoms, preferably acetic acid. The saidreaction is conducted in a volatile solvent such as a lower alkanol,preferably near its boiling point. tions are secured by reacting withthe alkylene polyamine salt of a monocarboxylic acid of the kinddescribed an amount of an aryl diepoxide sufiicient to substitute not Ifdesired, the re- Useful resins soluble in dilute acid solumore than oneepoxy group for each of the primary and secondary amino hydrogen atomsof the polyamine.

Aryl polyepoxy compounds useful in the production of the dilute-acidsoluble resins include compounds of the formula x X x 2 [1g Z1 1g 2 I LtH3 1t wherein R and R respectively represent hydrogen or an alkyl orphenyl radical; X represents hydrogen or a halogen; Z represents agroup; and n is or an integer of 1 to 2. Other aryl diepoxy compoundsuseful are those of the formula:

wherein Z has the aforesaid meaning. Examples of such aryl polyepoxycompounds are the diglycidyl ethers of the variousdihydroxydiphenylmethylphenylmethanes, and corresponding ethers of thedihydroxydiphenyldimethylmethanes, dihydroxydiphenylmethylethylmethanes,dihydroxydiphenylmethylpropylmethanes, dihydroxydiphenyl methanes,dihydroxydiphenylbutylphenylmethanes, dihydroxydi(chlorophenyl)methanesand dihydroxydi-(chlorophenyl)-dimethylmethanes; and the diglycidylethers of the O-, mand p-dioxybenzenes, such as hydroquinonediepoxypropyl ether. Commercial grades or mixtures of the foregoing canbe used.

' The alkylene polyamine salts useful in the production of the diluteacid-soluble resins effective for shrink-proofing wool include the saltsformed by reacting, while cooling to prevent vaporization of thesolvent, a solution of 1,2-diaminopropane, l,3-diaminopropane, or amember of the homologous series H2N(CH2CH2NH)11H wherein n is an integerfrom 1 to about 50, in a volatile solvent such as a lower alkanol, witha saturated monocarboxylic aliphatic acid having from 2 to 5 carbonatoms, such as acetic, propionic, butyric or isovaleric acid, in a molarratio such that all amino groups of the polyamine are converted to aminosalts. Complete neutralization of the amino groups is required in orderto secure acid-soluble resins by reacting stoichiometric proportions ofthe amino and epoxy groups.

The following examples serve to illustrate the invention:

Example 1 A resin soluble in dilute acids was made by reacting 180 gramsof di(1,2-epoxypropoxyphenyl)-dirnethylmethane, with 74 grams ofdiethylene triamine triacetate in 300 grams of boiling ethanol for 24hours. The solution was concentrated by evaporation of the solvent undervacuum, the concentrate containing about 58% of the resin, 38% ofethanol and 4% of water.

A wool-treating solution was made by mixing 170 grams of the saidconcentrated resin solution, 770 grams of water, grams of a non-ionicwetting agent being marketed under the trade name of Triton NE and 50grams of a 37% aqueous formaldehyde solution. This treating solution wasused to pad a quantity of wool flannel to a retention thereon of 75% ofits weight of the said solution. The flannel then was dried at 220 F.,heated 3 minutes at 300 F. to cure the resin, scoured with an aqueoussolution of a detergent, and dried untensioned. The weight of theflannel was increased 6% by this treatment.

The treated flannel and a piece of the untreated flannel previouslysoaked in water and dried, untensioned, was washed five cycles in avertical shaft type washing machine having a basket 13 inches indiameter oscillating 60 cycles per minute. Each cycle consisted of a 15minutes washing ess essentially comprises the following steps.

in a 0.5% aqueous solution of neutral soap at 120 F., and two subsequentwashings with 120 F. water during 15 minutes with the machine running.

Following five of such laundering cycles the treated flannel shrunk only1.5% in the warp direction and 1.2% in the filling direction, with noevidence of felting. The untreated flannel similarly laundered hadfelting shrinkage of 22% in the warp direction and 13% in the fillingdirection, and showed very severe felting.

Example 2 Following the procedure and using the materials described inExample 1, with the exception that 40 grams of di-(2,3-epoxypropyl)ether was substituted for the formaldehyde, wool flannel was padded withan aqueous solution containing 6% of the acid-soluble resin and 4% ofthe di-(2,3-epoxypropyl) ether.

The wool retained of its weight of the solution. The wool then was driedand the resin insolubilizedby heating at 220 F. during 15 minutes. Thethus treated wool and a piece of the untreated wool were subjected tothree laundering cycles as described in Example 1. The laundered treatedwool had shrunk 1.7% in the warp direction and 0.1% in the fillingdirection, whereas the shrinkage of the untreated wool was 14.6% (warp)and 9.5% (filling) in the laundering.

The acid-soluble polyamino polyhydroxy resins of the invention possessthe unexpected and unique property and important advantage that theresins can be exhausted from dilute aqueous solutions thereof upon woolimmersed in such solutions. The amount deposited can thus be closelycontrolled and objectionable excesses avoided. It has been found that ifwool or a Wool-containing textile article is warmed while immersed in amildly acidic solution of these resins, the resin is adsorbed on thewool surface and, when insolubilized thereon, either by heating or bytreatment with an aqueous solution containing a small amount, e. g.,about 1% to 5%, based upon the Weight of the dry article, of an alkalinecompound of the type hereinbeforedescribed, and of a small amount, e. g.1% to 5% of formaldehyde, glyoxal or a Water-soluble diglycidyl ether,based upon the dry weight of the article, the resin is converted in situto the insoluble state and confers upon the wool or article the propertyof resisting felting in laundering. This method has the importantadvantages over prior methods that it is applicable to wool in anydesired form, e. g., fibers, yarns, woven and knitted articles, etc. Thehand of the wool is not affected since inter-fiber bonding, the majorcause of the stiffening which occurs in squeeze roll treatments, isabsent. The entire deposition upon the wool surface occurs from verydilute aqueous solutions of the resin at moderate temperatures. The woolis not subjected to high temperatures, and relaxation shrinkage can beeliminated by controlling tension during drying.

Conveniently this immersion method of treatment of the wool orwool-containing article is conducted in simple apparatus of the typeused in dyeing the article, and preferably is applied thereto afterfulling and dyeing, and while the article is wet.

in this preferred modification of the invention the proc- The textilearticle'is wetted with water using a wetting agent of the nonionic type,with the Wetting liquid adjusted to a pH:

within the range between 3 and 6. The wetted article then is immersed ina mildly acidic aqueous solution of the acid soluble polyarnino,polyhydroxy resin until adsorption by the article is complete.Preferably this solution comprises water containing sufficient acid togive it a pH of 4 to 6, from about 2% to 12% of the said polyaminopolyhydroxy resin and from about 1% to about 5% of an insolubilizingagent which may be formaldehyde, glyoxal, or a simple water solublediepoxy compound such as diglycidyl ether, the percentages being basedupon the dry weight of the article. The acids used in the solution aresuch as form water soluble salts with the resins, suitable acids beingthe hydrogen halides and the saturated fatty acids having up to carbonatoms. The resin gradually is adsorbed by the article up to a maximumrequired to coat the fiber surfaces of the article after which no moreresin is taken up. Any excess resin is removed by immersing in waterbefore proceeding to the final step.

In a final step the thus treated wool or wool-containing article istreated, preferably at ambient temperatures, with a dilute aqueoussolution containing sufficient of an alkaline compound of the typehereinbefore described to give the solution a pH of at least '8. Thesolution also contains a small amount of an insolubilizing agent such asformaldehyde, glyoxal, or a water-soluble diepoxy compound such asdi'glycidyl ether. The alkaline compound and the insolubilizing agent,respectively, are present in an amount of around 1% to 5%, based uponthe dry weight of the article. This step of the treatment generallyrequires about 5 to 15 minutes.

The article then is rinsed with water until free from alkaline compoundsand excess insolubilizer, and is dried untensioned. After the finalrinsing the article is resistant to felting without further treatment.The usual finishing steps of softening, steaming, napping, decating, andthe like can follow, as desired.

,If desired, the wool article containing the absorbed and partiallyinsolubilized resin can be heated as a final step to cure the resin andimpart felt-resistant properties to the article, in the manner describedin Example 1.

The following examples illustrate this modification of the invention:

Example 3 A polyphenylolmethane mixture was made by reacting 590 grams(6 mols) of phenol at 30'35 C. with 81 grams of 37% formalin (1 mol ofHCHO) in the=presence of sufiicient concentrated hydrochloric acid toreduce the pH of the mixture below zero until all of the formaldehydehad reacted. Excess phenol was distilled off under 50 mm. of mercurypressure at below 165 C. The residue of about 180 grams consisted ofapproximately two-thirds by Weight of a mixture of isomericdiphenylolmethanes and about one-third of higher molecular analogousstructures containing three and four phenyl rings. The aforesaiddistillation residue of mixed polyphenylolmethanes (about 180 grams) wasreacted with 550 grams (6 mols) of epichlorohydrin and 180 grams of a50% aqueous solution of caustic soda at 5060 C. during about 2 hours.Excess epichlorohydrin then was distilled off under vacuum attemperatures below 60 C., the mixed polyepoxypropyl ethers ofpolyphenylolmethanes separated as a viscous liquid having an equivalentweight of 171 grams per epoxy group. This product comprised abouttwo-thirds by weight of diepoxypropyl ethers of mixed diphenylohnethanes(mostly 2,4fand 4,4'--isomers) and about one-third of the triepoxypropyland polyepoxypropyl ethers ofmixed polyphenylolmethanes containing threeor more benzene nuclei, all phenolic hydroxyl groups being reacted toform epoxypropyl groups.

A water-soluble polyamino polyepoxy resin was produced by adding 760grams (4.4 equivalents) of the aforesaid mixed polyepoxypropyl ether ofdiphenylolmethane, diluted with 76 grams of methanol, during 2 to 3hours to a boiling solution of 283 grams (1 mol) of diethylene triaminetriacetate in 700 parts of methanol. The boiling was then continueduntil, upon testing, the resin formed a clear solution with ten timesits volume of water. It was cooled and 120 grams of glacial acetic acidwere added thereto to stabilize the resin solution and increase itsuseful storage life. The solution now contained about 50% of the resin.The addition to the resin of a quantity of an aliphatic saturatedmonocarboxylic acid having 2 to 5 carbon atoms, in excess of thatrequired to form salts with all of the amino groups present, iseffective as stabilizer for the resin. Commercially adequate storagelife is obtained by the addition of one or two mols of such organic acid'per mol of the polyamine used in making the acid-soluble resin.

All-wool socks grams), were wetted with a dilute aqueous solution ofacetic acid having a pH of approximately 5. The wetted socks then wereimmersed in an aqueous solution at pH 5, containing 5000 grams of Water,5 grams of the said polyepoxy resin, 0.6 gram of acetic acid, 2 grams offormaldehyde (as HCHO) and 4.6 grams of methanol. The solution and sockswere maintained at 70 C. until no further resin was adsorbed by thesocks. This was determined by taking aliquot samples of the solution atintervals, precipitating the resin therein with caustic alkali, anddetermining gravimetrically the resin present in the sample. The sockswere rinsed with water, then immersed for 5 minutes in cold watercontaining 1 gram of sodium carbonate and 1 gram of formaldehyde, andfinally rinsed and dried untensioned.

The treatment rendered the wool less sensitive to alkalies, as shown bya reduction in the percentage of matter soluble in alkalies from 11.4%on untreated socks to 8.0% on the treated socks, according to the testdescribed in Federal Catalog CCC-T-l91a, Supplement, 1945, section VII,paragraph 3 (Supt. of Documents).

The thus treated socks, and a quantity of the untreated socks, soaked inwater and dried untensioned, were washed ten cycles using the proceduredescribed in Example 1.

The treated socks had a shrinkage of 2.5% measured on the foot length,with no evidence of felting. 1 The untreated socks after similar washingand drying untensioned showed 15% shrinkage and very serious felting.The hand of the sockswas not noticeably affected by the treatment.

Example 4 All wool shirting cloth about 10 ounces per yard unit weight(900 grams) was wet out with an aqueous solution containing a non-ionicwetting agent marketed as Triton NE and adjusted to pH 5. The cloth wasthen heated to the boil in one hour in 8,000 grams of an aqueoussolution containing 13 grams of the polyamino polyhydroxy resin solutiondescribed in Example 3, two grams formaldehyde and 8 grams Triton NE.After complete adsorption of the resin by the cloth in 80 minutes thecloth was rinsed thoroughly and treated .for 10 minutes with a coldaqueous alkaline solution containing 10 grams sodium carbonate and 10grams formal dehyde. The cloth then was rinsed with water and dried atF. untensioned. The finished cloth had a soft pliable hand similar tothat of the untreated cloth. It had shrinkages of 3.4% and 1.7%,respectivelyv in the warp and the filling directions after a launderingtest according to Federal Specification CCC-T-1'91b Textile TestMethods, Method 5554, Supt. of Documents, May 15, 1951.

The cloth increased 4% in weight as the result of the resin treatment.

Example 5 Ten grams of polyethyleneamine of the formula H(NHC2H4)nNH2having an average molecular weight of 1800 was dissolved in 60 grams ofmethanol and was carefully neutralized (to bromophenol blue) with 30grams of butyric acid. This solution then was boiled with 60 grams of1,1-bis-(1,2-epoxy-3-propoxyphenyl) butane (mixed paraand ortho-isomers)having an equivalent weight of 230 grams per epoxy group until thesolution was miscible with ten times its weight of water. After thefurther addition of 15 grams of butyric acid to serve as a stabilizer,the solution contained 44% of the resultant resin.

Wool flannel (70 grams) previously wet with water and adjusted to pH 5.2with dilute butyric acid was heated to boiling 2 hours in an aqueoussolution containing 9.8 grams of the aforesaid resin solution, 1 gram offormaldehyde and about 1990 grams of water, and adjusted to pH 5. Thewool then was rinsed with water, and was immersed in water containing 1%of sodium carbonate and 1% formaldehyde, based on the dry weight of theflannel, and then was rinsed and dried untensioned.

Following a severe laundering for 1 hour at 140 F. using the apparatusand method described in Example 1, the treated flannel had shrunk 2%,whereas the untreated flannel had shrunk 15 as a result of the samelaundering.

Example 6 Para-bis 1,2-epoxy-3 -propoxy-ortho-chlorophenyl methane (99grams) was boiled with 70 grams of diethylene triamine triacetate in 100grams of methanol until miscible with 10 times its weight of water. Then30 grams of glacial acetic acid were added as a stabilizer. A mixture of8.3 grams of this polyamino polyepoxy resin solution and 3 grams of a37% formaldehyde solution was diluted to 2000 grams with water.

Wool flannel (100 parts), wetted and adjusted to pH 5 with acetic acid,was immersed in this solution and heated 2 hours at 70 C., the resinbeing substantially completely adsorbed. The cloth was rinsed and thentreated with a cold aqueous alkaline formaldehyde solution containing 1%of sodium carbonate and 1% formaldehyde, based upon the weight of thedry flannel.

After drying the treated flannel untensioned, and laun dering the samefor 2 hours at 140 C. in the general manner described in Exampe 1, theflannel shrank 3%, whereas the untreated flannel shrank 15% after thesame laundering.

Example 7 A length of a 16 ounce shirting approximately 4.75 yards long,of mixed fiber content 90% wool and nylon, weighing 5.1 pounds, wasrinsed with 300 pounds of water containing 0.4 ounce of a non-ionicWetting agent of the substituted polyethylene glycol type. The cloththen was heated at 70 C. for 6 hours in 300 pounds of an aqueoussolution containing 10.6 ounces of the 50% resin solution described inExample 3, 3.3 ounces of a 37% aqueous formaldehyde solution and 0.4ounce of the said non-ionic wetting agent, corresponding to 6.8% of theresin and 1.9% of formaldehyde, based upon the weight of the cloth.After cooling and rinsing off any excess resin solution the cloth wastreated with a cold aqueous solution containing 0.65 ounce of sodiumcarbonate and 1.6 ounces of 3% formalin, rinsed, and then treated with acold aqueous solution containing 0.1 ounce sodium stearate, againrinsed, the pH adjusted to 6, and the treated shirting dried.

In a laundering cycle described in Federal Specification CCC-T-l9lb,Supt. of Documents, May 15, 1951, as method'5554, after relaxation asper method 5558, applied to samples of the treated and untreatedshirting, the following results were secured:

Felting Shrinkage, Percent Warp Filling Untreated cloth 12. 1 8. 2Treated cloth 3. 0 '0. 3

Example 8 Shrinkage, Percent Warp Untreated flannel Treated flannelFilling The invention is susceptible of modification within the scope ofthe appended claims.

I claim:

1. Process for improving the properties of wool-containing textilematerials and rendering the same resistant to felting and shrinkage inlaundering, which comprises heating said material in a dilute aqueoussolution having a pH within the range from 3 to 6 and containing (A) awater-soluble resinous product of the reaction of (1) a neutral salt ofan alkylene polyamine with a saturated aliphatic monocarboxylic acidhaving from 2 to 5 carbon atoms and (2) an aryl polyepoxy compound ofthe class consisting of those having the formula X is selected from theclass consisting of hydrogen and the halogens; Z designates a group; andn is zero or an integer of 1 to 2; and curing the resin in situ on thetextile material, and at some stage prior to the completion of thecuring step, treating the textile material containing said resinousproduct with an insolubilizing agent selected from the class consistingof formaldehyde, glyoxal and the water-soluble aliphatic digiycidylethers.

2. Process for improving the properties of wool-containing textilematerials and rendering the same resistant to felting and shrinkage inlaundering, which comprises heating said material in a dilute aqueoussolution having a pH within the range from 3 to 6 and containing (A) awater-soluble resinous product of the reaction of (1) a neutral salt ofan alkylene polyamine with a saturated aliphatic monocarboxylic acidhaving from 2 to 5 carbon atoms and (2) an aryl polyepoxy compound ofthe class consisting of those having the formula cals; X is selectedfrom the class consisting of hydrogen and the halogens; Z designates agroup; and n is zero or an integer of 1 to 2; and (B) an insolubilizingagent selected from the class consisting of formaldehyde, glyoxal andthe water-soluble aliphatic diglycidyl ethers, and thereafter curing theresin in situ on the textile material.

3. Process for improving the properties of wool-containing textilematerials and rendering the same resistant to felting and shrinkage inlaundering, which comprises heating said material in a dilute aqueoussolution having a pH within the range from 3 to 6 and containing (A) awater-soluble resinous product of the reaction of (1) a neutral salt ofan aliphatic alkylene polyamine with a saturated aliphaticmonocarboxylic acid having 2 to 5 carbon atoms, and (2) an arylpolyepoxy compound having a structure corresponding to the formula X isselected from the class consisting of hydrogen and the halogens; Zdesignates a radical; and n is zero or an integer of 1 to 2; saidaqueous solution also containing an insolubilizing agent for (A)selected from the class consisting of formaldehyde, glyoxal and thewater-soluble aliphatic diglycidyl ethers; and thereafter treating thethus impregnated textile material with a dilute aqueous solutioncontaining an alkaline watersoluble compound in amount at leastsufiicient to give the solution a pH of at least 8.

4. Process for improving the properties of wool-containing textilematerials and rendering the same resistant to felting and shrinkage inlaundering, which comprises heating said material in a dilute aqueoussolution having a pH within the range from 3 to 6 and containing (A) awater-soluble resinous product of the reaction of (l) a neutral salt ofan alkylene polyamine with a saturated aliphatic monocarboxylic acidhaving from 2 to carbon atoms and (2) an aryl polyepoxy compound of theclass consisting of those having the formula the halogens; Z designatesa CH2CHCH20 group; and n is zero or an integer of 1 to 2; and (B) aninsolubilizing agent selected from the class consisting of formaldehyde,glyoxal and the water-soluble aliphatic diglycidyl ethers, andthereafter treating the thus impregnated textile material with a diluteaqueous solution containing at least around 1% of an alkaline alkalimetal 10 compound and at least around 1% of formaldehyde, both basedupon the dry weight of the material.

5. Process for improving the properties of wool-containingtextilematerials and rendering the same resistant to felting and shrinkage inlaundering, which comprises heating said material in a dilute aqueoussolution having a pH Within the range from 3 to 6 and containing (A) awater-soluble resinous product of the reaction of (1) a neutral salt ofan aliphatic alkylene polyamine with a saturated aliphaticmonocarboxylic acid having 2 to 5 carbon atoms, and (2) a polyglycidylpolyether of a dihydric phenol having a 1,2-epoxy equivalency greaterthan 1.0; said aqueous solution also containing an insolubilizing agentfor (A) selected from the class consisting of formaldehyde, glyoxal andthe water-soluble aliphatic diglycidyl ethers; and thereafter treatingthe thus impregnated textile material with a dilute aqueous solutioncontaining at least around 1% of an alkaline water-soluble compound andat least around 1% of formaldehyde, both based upon the dry weight ofthe textile material.

6. Wool-containing textile material resistant to felting and shrinkagein laundering, the fibers forming said material having on their surfacesa water-insoluble composition comprising the insolubilized water-solubleresinous product of the reaction of (1) a neutral salt of an alkylenepolyamine with a saturated aliphatic monocarboxylic acid having 2 to 5carbon atoms, and (2) an aryl polyepoxy compound of the formularadicals; X is selected from the class consisting of hydrogen and thehalogens; Z designates a OHzCHCHzO- group; and n is zero or an integerof not more than 2.

References Cited in the file of this patent UNITED STATES PATENTS2,537,064 Kropa et al. Jan. 9, 1951 2,539,958 Maaskant Ian. 30, 19512,632,717 Landolt Mar. 24, 1953

1. PROCESS FOR IMPROVING THE PROPERTIES OF WOOL-CON TAINING TEXTILEMATERIALS AND RENDERING THE SAME RESISTANT TO FELTING AND SHRINKAGE INLAUNDERING, WHICH COMPRISES HEATING SAID MATERIAL IN A DILUTE AQUEOUSSOLUTION HAVING A PH WITHIN THE RANGE FROM 3 TO 6 AND CONTAINING (A) AWATER-SOLUBLE RESINOUS PRODUCT OF THE REACTION OF (1) A NEUTRAL SALT OFAN ALKYLENE POLYAMINE WITH A SATURATED ALIPHATIC MONOCARBOXYLIC ACIDHAVING FROM 2 TO 5 CARBON ATOMS AND (2) AN ARYL POLYEPOXY COMPOUND OFTHE CLASS CONSISTING OF THOSE HAVING THE FORMULA